Shellac-polyglycol reaction products and method of making same



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PATENT? OFFICE SHEILAC-POLYGLYOOL REACT ION PROD UO'IS AND METHOD OF MAKING SAME William 'Howlett Gardner, Bayside, and Henry Hail Bassiord, In, Brooklyn, N. Y., asaignora to U. 8. Shellao'lm Association, Inc.,

York, N. 1., a corporation of New York No Drawing. Application May 28, 1942,

" Serial No. 444.923

8 Claims. (Cl- 280-404) This invention relates to new compositions of matter prepared-by reacting shellac with poly-'- glycolsandtotheuseofthesecompositionsin aqueous paints and varnishes.

This application is a continuation in part of our copending case Serial No. 032,456, filed April solution for the purpose oi. modifying the brittleness of the films. Even the water-soluble plasticisers, such as glycerine, for instance, but temporarily improve the flexibility oi the films, and to a limited extent only.

Another weakness of films prepared using aqueous solutions of shellac and other binders. such as gelatlne, glue. dextrine, starch and the like is their poor water resistance.

It is well known that shellac is insoluble in water and aqueous acids and that it is precipitated from its aqueous alkaline solutions by acids. In consequence, shellac can be, used in neutral aqueous solution only in the term of its soapsand cannot be used at all in acid solutions having a pH less than 5 or inconiunction with other resin solutions which havea'strong acid reaction; But acid solutions oi modified shellac resins 'oiier special promise'ior blending which requireanacidsetting agent.

' likewise, solutions oi modified shellac resin in m n I I t 101' mm M m be use m Aqueous paints andinksmaybeprepared by addwhich it has been round undesirable to use-aikalino solubilizingagents as i'or example:

Where the alkaline solution reacts with the vesselusediordissolvingtheshellacthusshorten An object. therefore, oi-our invention is the.

preparation oi reaction products or shellac or shellac derivatives and p lyslyools. The second obiectis the preparation oifa modified with other 1 object is the preparation of shellac derivatives which are soluble in water without the use of alkaline dispersing agents and which are not precipitated therefrom by either acids or alkalies.

solutions containing shellac polyslycol reaction products which shall yield permanently flexible fiims'on evaporation. v

The first object can be attained by" heating shellac or a shellac derivative with a polyglycol of the formula:

H- (O-CsH4)'aOH where n is an integer equal to or greater than 2,

15 such as. diethylene glycol (n=2), triethylene glycol (n=3), polyglycols of average molecular weight 400, (average value or n=8.'1); MW 1500, in -34); MW 4000, (n-90); either alone or in thepresence 01' a condensation catalyst such as p-toiuene sulfonic acid. Shellac as referred to above and elsewhere 111 this application, includes all iorms oi lac. the secretion oi theinsect.

Tachardia la'cca Kerr, whether in raw, refined or manufactured forms. Shellac derivatives include the monomeric acids obtained by hydrolysis or shellac such as aieuritlc and shellolic acids.

Alternatively the shellac or shellac derivative may first be heated with a polyhydric alcohol in ing Tlexible lac compositions" and the product obtained iurther reacted with a polyslycol. The

\ ik second and third objects can be accomplished by condensing shellac or a shellac derivative with a polygly'col oi molecular weight oi. about 1500 or ing suitable pigments, extenders, toners, and the like to these varnishes.

7 tion such as brushing, spraying, dipping, etc. Detached films are readily obtained by flowing the paint or varnish'onto a mercury surface, andallowlngtheiilmtodry. Thedryfilmcan 50 then be liited iree oi the mercury.

I have found that, in order to form a fusible, soluble. product, the weightoi 90138 7 01 used should be at least 10% or the weight of the shellac because alowerproportion oi polyglycol rqinsolubl'einhydrocarbon solvents. 'ihetliird II does not produce the desired results. Smaller The fourth object is the preparation oi aqueous accordance with the process described in our co- 3o pending application, serial No. 332,456, describ- Fllms-onpaper, metal, glass, cloth or other,

suriaces may bepreparedusing these varnishes 4 5 and paints, by the usual 0! appllcaproportionsor' .polyglycol invariably result in the formation of an insoluble, infusible gel. No upper limit exists, however, for the weight of polyglycol which may be used in the reaction vessel, although the amount of polyglycol which can chemically combine with the shellac is limited by the number of reactive hydroxyl and carboxyl groups in the shellac molecules.

Proof that shellac reacts chemically with polyglycol 1500 is found by reference to ExampleIll below. The reaction between the condensation asazaee weeks aging. Detached films prepared by evapcrating a thin layer of the aqueous ammonia varnish on a mercury surface, floating or not floating as in the case of a mercurized metal .plate employing copper for the plate or heated f'surface, were flexible and possessed moderate components takes place rapidly at temperatures of 120 C. and above and is usually evidenced by the appearance of froth due to the water evolved by the reactions taking place.

Those products which are water insoluble are usually soluble in alkaline aqueous solutions containing ammonia, sodium carbonate, borax, sodium silicate, sodium phosphate, or aqueous solutions containing organic substances possessing a strong alkaline reaction such as morpholine, triethanolamine, ethylamine and the like. These water insoluble, alkali soluble prod-' ucts can be readily purified by filtering the aqueous alkaline solutions to remove wax, dirt and gelled material. The resin can then be precipitated by acidifying the solution, and the precipitate filtered and washed free of excess reactant and water soluble impurities,

It has been found that the products obtained by reacting shellac with polyglycols of high molecular weight are not only completely soluble in pure water but have the unique characteristic of also being completely soluble in benzene. They have therefore been found to possess ex-- cellent detergent and emulsifying properties. They can be readily blended in emulsion varnishes of the type described earlier in this application, and, due to their mutual solvent action on hydrocarbons and water, tend to stabiliae the emulsion. Furthermore, by using materials of this type, clear varnishes containing water and hydrocarbon solvents can be pre pared.

The following examples in which parts are given by weight, are illustrative oi the instant invention without, however, limiting the same to any oil? the specific embodiments, amounts or conditions there recited.

Eromple l Add its parts of dewaxed shellac gradually over a 30 minute period to 120 parts of a mixture of polyglycols, whose average molecular weight is about 400 (poly allrylene oxide #400), and which contain 1 part of .p-toluene sulionic tensile strength and toughness when prepared fromthe shellac-polyglycol reaction product, but

acid catalyst. During the addition, agitate the reaction mixture vigorously and maintain the temperature between its and 155 G. After all in this manner, indilute aqueous ammonia.

Films obtained by evaporation of this solution possessed good adhesion to paper, glass and metal, and those in paper and metal were much crumbled and fell to pieces when made from shellac.

Example ,II

In this example a modified shellac, (prepared by condensing seed-lac with a polyhydric alcohol in accordance with the process described in our copending application, Serial No. 332,456 describing Flexible lac compositions) is reacted with a high molecular weight polyglycol. The modified shellac-polyhydric alcohol product is prepared as follows: 81 parts of ethylene glycol are heated to' 0.; 0.5 part of p-toluene sulfonic acid are then added and 220 parts of seed lac areadded gradually with goodagitation as rapidly as it dissolves; the temperature is maintained throughout the addition between 120 and 150 C.; the addition requires about one-half hour; after 10 minutes additional heating and stirring the reaction is apparently complete as evidenced by cessation of foaming. I This modified shellac, without further treatment, is then added portionwise to 100 parts of polyglycol of average molecular weight 1500. The resulting mixture forms a uniform melt at C. and said mixture is stirred and heated for one hour at -160 c,

The resulting product may then be dissolved in 800 cc. or water containing 30 parts of sodium carbonate and freed of wax and other impurities by filtration. The product is recovered from the alkaline filtrate by pouring into 50 parts of 5% aqueous acetic acid, whereupon the shellac reaction product precipitates as a gummy adherent resin which is recovered and washed by decontation. v

Films yielded by the aqueous ammonia solution of the resin show'improvement over comparable films obtained from ammoniacal solutions of both untreated and polyhydric alcohol modified shellac.

Example H! heated for 2%., hours between and 200 C. I

The resulting product should be completely soluble in water.

A product prepared in this manner was found to be completely soluble in water, in strong and dilute aqueous hydrochloric acid, acetic acid and I ammonium hydroxide. It was also readily soluble in many organic solvents such as acetone, dioxane, ethyl alcohol, benzene and chloroform;

Proof that chemical reaction has occurred between the shellac and polyglycol 1500 may be demonstrated by the following simple experiment in which it is shown that a physical mixture of shellac and the polyglycol is not completely water soluble.

1'3 parts of shellac are dissolved m 100 parts of po yslycol 1500 at a temperature of less than 100 C., and in the absence of catalyst. When this resin separates which gradually hardens as the water extracts the po y lycol therefrom. The weight 01 dry, water-insoluble resin recovered is exactly equal to the weight of the shellac previously dissolved in the polyglycol. It is therefore evident from the above examples that when shellac and polyglycol 1500' are heated together at elevated temperatures in the presence of a catalyst, as described in the first paragraph or this Example III, a reaction takes, place which converts the shellac to a new water soluble resin.

Having described our invention, what we claim and desire to secure by Letters Patent is as follows:

i. A water-soluble shellac product which is not precipitated by acids, obtained by reacting shellac with a polyglycol of average molecular weight or product is added to pure distilled water, a gummy 1500, the polyglycol being at least 10% of the A weight or the shellac.

2. A shellac product made by reacting about 220 parts of shellac and at least 80 parts of ethylene glycol at a temperature of approximately 120- 150 C., and further reacting said product with about 100 parts 0! a polyglycolof a. molecular W ht of pproximately 15 0, at a temperature of approximately 150-160" c .3. A shellac product made by reacting shellac and a polyglycol of a molecular weight or approximately 1500. at a temperature of approximately 180-200 C. the polyglycol being at least 10% of the weight of the shellac.

, parts of ethylene glycol, at'a temperature of approximately l50 C., and further reacting the said product with about 100 parts of a polyglycol having a molecular weight of about 1500, at a temperature of -160" C.

6. A- method of preparing a resin which is not precipitated by acids, which comprises a reacting shellac with a polyglycol of a molecular weight of about 1500 at a temperature of approximately mil-200 C. the polyglycol being at least 10% of the weight of the shellac.

7. A method of preparing a resin which is not precipitated by acids, which comprises reacting about 13 parts of dewaxed shellac with about 100 parts of a polyglycol having a molecular weight of about 1500'.

8. A method of preparing a resinwhich is not precipitated by acids, which comprises reacting about 13 parts of dewaxed shellac with about 100 parts of a polyglycol having a molecular weight of about 1500, at a temperature of approximately 180-200 C.

WILLIAM HOWLETI GARDNER. HENRY HAIL BASSFORD, J'R. 

